Alkoxynaphthalimidothiazolium salts,useful as optical bleaching agents

ABSTRACT

COMPOUND OF THE FORMULA:   2-(B(+)-X-),6-(R-O-)-2,3-DIHYDRO-1H-BENZ(DE)ISOQUINOLINE-   1,3-DIONE A(-)   IN WHICH R IS AN ALKYL RADICAL, OR A HYDROXY OR ALKOXY SUBSTITUTED ALKYL RADICAL, SAID ALKYL HAVING ONE TO FOUR CARBON ATOMS, X IS A DIRECT LINKAGE OR P-PHENYLENE, B&amp; IS AN N&amp;-(LOWER ALKYL) CYCLOAMMONIUM GROUP IN WHICH THE CYCLAMMONIUM GROUP IS THIAZOLIUM AND IS ATTACHED TO X THROUGH A CARBON ATOM, THE REMAINING CARBON ATOMS IN B&amp; BEING UNSUBSTITUTED OR SUBSTITUTED BY CHLORINE , LOWER ALKYL, PHENYL, OR METHYLTHIO GROUPS, AND A&amp; IS A COLORLESS MONOVALENT ANION. THESE COMPOUNDS CAN BE USED AS FLUORESCENT BRIGHTENING AGENTS FOR FIBERS BASED ON ACRYLONITRILE POLYMERS OR COPOLYMERS.

ave c -2 0 R, 1

substituent 3,804,837 ALKOXYNAPHTHALIMIDOTHIAZOLIUM SALTS, USEFUL ASOPTICAL BLEACHING AGENTS Georges Raymond Henry Mingasson, Paris, andAnnick Marthe Suzanne Simone Domergue, Eaubonne, France, assignors toUgine Kuhlmann, Paris, France No Drawing. Original application Aug. 9,1968, Ser. No. 751,349, now Patent No. 3,649,633. Divided and thisapplication Dec. 1, 1971,Ser. No. 203,873

Claims priority, applicfitgo rlzgrance, Aug. 11, 1967,

Im. Cl. c4374 91/30 a whims 5 AB'S'lRACTbF Tl- IE DISCLOSURE v Compoundof the formula:

in which R is an alkyl radical, or a hydroxy or alkoxy substituted alkylradical, said alkyl'having one to four carbon atoms, X is a directlinkage or p-phenylene, B

is an N -(lower alkyl) cycloammonium group in which the cycloammoniumgroupis thiazolium' and is attached 'to X through a carbon atom, theremaining carbon atoms in B being unsubstituted or substituted bychlorine, lower alkyl phenyl, or methylthio groups, and A isa colorlessmonovalent anion. These compounds can be used ,acrylonitrile polymers orcopolymers.

. (I) "in which R-represents analkyl radical, B represents acycloammonium "group and A represents 'a colorless 'monov'alent' anion.'i

The radical R- isfpreferably 'a'n' al-kylg radical containing "from- 1to-4 carbon atoms for example, methyljetliyl,

propyl or isopropyl groups; These radicals ma 'stitute'd by at least onenon-chromophore a'nd in n such as for ex mple "ahydroxy or ABy-cy'cloainmoiiium group is meant a mono orpolycyclic heterocyclicgroup containing one for more hetero atoms, the hetero atomor' onefofthe hetero atoms being a'quaterriarynitrogeu'atom. Examples of suchgroups are pyridinium "'imidazolium, 'benzimida'zolium' 'pyrazolium,

pyrazoliniuni 'triazoliuin', thiazolium, benzothiazolium oxazolium,isoxazolium, benzo-oxazolium, oxadiazolium, thiadiazolium, quinolium andindazolium rings. These States Patent Patented Apr. 16, 1974 rings maybe substituted byat least one non-chromophore and non-anionicsubstituent. They may be attached through "a carbon atom tonaphthalimido group either by a direct linkage or by a p-phenyleneradical.

The cationic organic compounds of the invention are salts which aresoluble in water, and their aqueous solutions show an intense green-bluefluorescence. They have a good afiinity for synthetic fibres based onacrylonitrile polymers or copolymers, with which they form truecompounds, the cations being attached at the negative positions of thefibre. They impart to the acrylic fibres a remarkableeffect of whitenesswhich persitsts on re- 7 peated washing and is stable to light andsteaming and as fluorescent brightening agents for fibres based on afwhich R has the meaning given above and B represents "fast to chlorine.

known. Anselm and Zuckmeyer (Ber., 1899, 32, p. 3291) have prepared4-methoxy N methylnaphthalimide.

-Alkoxylated derivatives of naphthalimides are already Similarly FrenchPats. Nos. 1,322,849 and 1,344,883 and -'U.S; Pat. No. 3,310,564describe 4-alkoxy-naphthalimides in which the nitrogen atom issubstituted by hydrocarbon radicals. These substances are insoluble inwater, which makes their application complicated owing to the fact thatthey, have to be very finely dispersed. Those which have'a fluorescentbrightening action an acrylic fibres owe it to absorption by the fibre,but not to a true chemical combination with the latter.

The compounds of Formula I can be prepared for 65:- ample by reacting analkylating agent of formula A- alkyl wherein A has the meainng givenabove, for example-an alkyl halide, sulphate or sulphonate, with acompound of the general formula:

N-B' 00 be i a heterocyclic, monoor poly-cyclic group containing one ormore atoms of nitrogen or one or more hetero-atoms one of which is anitrogen atom, possibly in the presence of a solvent such as for examplean aromatic hydrocarbon "or a chlorinated derivative thereof, an alcoholor dimethyl it formamide. The preferred alkylating agent is an alkyl "1'I sulphate such as, for example, methyl sulphate.

- The compounds of Formula II may be obtained for Qexamplebyaany ofseveral known processes, for example by the condensation of a4-alkoxy-naphthalic anhydride, and especially4-methoxy-naphthalicanhydride (C. 1926,

II, p. 2817--J. Chem. Soc. 1939, p. 792), with a heterothe formula:

cyclic primary-amine of B'NH (III) in which B has the meaning givenabove.

, It isalso possible to prepare the compounds of Formula 'll from l-bromo-naphthalimides of the formula:

NQB' 06 CO in' 'which has the meaning given above. These naphthaliinides'may be obtained by condensing 4-bromo-naphthalic anhydride,prepared by the method of Rule and of Formula III by a process describedby Bradley and Pexton (J. Chem. Soc., 1954, p. 4435). This condensationis preferably carried out in a solvent such as for example water,alcohol or a hydrocarbon, at atempera- Thompson (J. Chem. Soc., 1937, p.1764), with a. amine ethylene glycol by heating the mixture for hours at130.-140 .C. After. cooling, the-precipitate is filtered 01f, washedwith water and dried. 17.4 parts of 4-bromo-N-(2-pyridyl)-naphthalimide,"melting at 247-248 C. are obtained, of theformula:

.ture between 100 C. and 200 C. Ethylene glycol and 5 diethylene glycol,which can be used in a very wide range x N of temperature, areparticularly suitable solvents. The 0G 0 bromonaphthalimides of FormulaIV can then be con- I l I I verted into alkoxynaphthalimides of theFormula H, I 4 owing to the mobility of the bromine atom. This propertyI 'is pointed out by Graebe (Liebigs Ann., 327, p. 87) and by Bradleyand Pexton (J. Chem. Soc., 1954, p. 4434). I r g I For this conversionthe bromonaphthahmrdes of Formula 1r Br 1 2 IV ma be treated in anexcess of alcohol ROH at the I EXamP r V boiling point or under pressurewith an alkali metal alco- A mlxture of 27 parts 011;lll-armno-g,i-dmethglgrggazolf, of R has given above and Me is an alkalimetal, preferably sodium. 0 T og; ,tate is filtered washed with Thequaternary salts of Formula I are very soluble in to g gi of 4Jbromo N sdimethyl 4 water, and their solutions are extremely fluorescent in wa eran 16 pyrazolyl)-naphthal1rmde, meltmg at 267 C., are obdayhght andstill more under the lnfluence of ultraviolet tamed, of the formula.rays. They may be applied to fibres based on acrylonitrile CH3 polymersor copolymers such as those sold under the CO N trade names Orlon,Courtelle, Crylor, or Dralon, Br-Q either by dyeing in a bath having apH of from 4 to7 or I by any other process such as for examplethermo-fixation Q CNH or incorporation in the mass during spinning. Avery small I CO g, g i of the P f the to 04% 1s 3 On replacing theZ-aminopyridine in Example 1 with su cient to obtain an exce lent witemng effect. other heterocyclic amines NH d operat ng in a Thenaphthahmldes of the Formulae II IV are new similar way, the followingbromo-naphthalimides are obcompounds but for the most part they haveweak fluoi d; I

- M.P. Example B'NH: Naphthallmides ofFormulaIV 3-an1ln py d14-bromo-N-(3-pyridy1)-naphthalimlde. 217 2-a1nmo4-bromo-N-(6-methyl-2-pyrldyl)-naphthalimide.- 238-b!0m0-N-(2-thiazolyl)-naphthalimlde 984-bromo-N-(4-methyl-2-thlazolyl)-naphthalimlde.-. 2484-bromo-N-(Z-benzothlazolyl)-na.phthallmide 3004-bromoN-(2-phenyl-fi-benzothiazolyl) -naphthallmlde. .3084-bromo-N-[4-(2-benzothiazolyl)-phenyl]-naphthalimlde. 3264-br0m0-N-(2;benzoxazolyl)-napl1thalin1lde 2 4-b r0mo- N-(3-methyl-5isoxazolyl) -naphthalimlde 94-bromo-N-(2-methyl-6-qulno1yl)-napthallmlde-..- 8-br0mo-N-(2benzlmidaz0lyl)-naphthallmide. 335 ethyl-hen azol 4-bromo-N-,2dlmethyl-6-benzimidazolyD-naphthallmlde.-. 325 4-amino-2-phenylbenzlmidazole4-bromo-N-[4-(2-benzimidazolyl)-phenyl]-naphthalimlde 31ggfilgoiggggrfi-l-methyl-benzirnidazole.. tgromo-llg-g-gl-(iintlliylliz-berlilzifiniihglyl)-phenyl]-naphthallml romo- -n azo 7 -na tai e.;...t..;...-. 18... 3-amino4ichlorolndaz le 4 br0mo-N-(fi-chloro-aindagnlyl)-naphthallmide 324*bromo-N-(5-methylthlo-2-thiadlazolyl)-naphthallmide; 2404,-br0mo-N-(4-phenyl-3-pyrazolyl) 'naphthallmide .L7. 2984-b10m0-N-(5-phenyl-3-pyrazolyl)qmphthallmide 2864-bromo-N-(.S-methyl--phenyl-a-pyrazolyl)-naphthalimlde 3024;amln0-3-methyl-5-phenyl-pyraz0le. 4-bromo-N-(3-methyl-5-phenyl-4-pyrazolyl) -naphthalimide 254 -D Y 3 y -Dyrazole.4,-bromo-N-{4-(3,5dtmethyl-1-pyrazolyl)-phenyl]-naphthallmlde 245 ggg21$ggi-glicirglgigggimethyl-AZ-pyrazohneZ13romo-g-(i-giifiifrimetliiyl-liAz-pyfiafioggl)-phenyl]-naphthalimlde-.53g

.- romo- -trlazo -3- -na t a do...

antrans ateti ear a eli r-ma as a u Z e romo- 1, -4 -triazo-4 -na t de4'-amlno-3-pheny1-5-methyl-1.2,4-4H.4-bromo-N-l4-(5-methyl-1,ZAjH-trlziol-3-yl)-pheny11-naphthallmlde..-.-300 rescent properties and an afiinit for fibres-which is too 'small tohave an optical bleaching effect of any interest.

In these circumstances it was unexpected that the conversion of thenaphthalimides of Formula II into their quaternary derivatives wouldconsiderably increase the fluorescence of these compounds.

The following Examples 1 'to 61 illustrate the preparation of theseintemediate products. Examples 62 to 84 NAPHTHALIMIDES OF FORMULA IVExample 1 14 parts of 4-bromo-naphthalic anhydride are condensed with5.2 parts of 2-aminopyridine in 100 parts of NAPHTHALIMIDES OF FORMULAII Example 30 4 parts of sodium are dissolved in'1250, parts by volumeof methyl alcohol in an apparatusprovided with a stirrer and a refluxcondenser. Then 14.12 parts of 4-bromo-N- (2-pyridyl)-naphthalimideare..added and the mixture is heated under reflux for 3 hours. Thereaction mixture thickensand becomes a pale yellow color. After cooling,the precipitate is filtered otf, taken up in dilute acetic acid,.filtered and washed with water, then with alcohol.,JAfter drying, 11.3parts of 4-methoxy-N-(2-pyridyl)-naphthalimide of melting point 240 C.are obtained. On-recrystallizing from amixture of alcohol and dimethylformamide, the product forms long yellow needles melting at 242 C.

By the application of the same process to the 4-bromonaphthalimides ofExamples 2 to 29, the corresponding 4- methoxy-naphthalimides areobtained, the melting points of which'are given.

easaaseese samene s...

Example 53 I A mixture of 11.4 partsof 4-methoxy-naphthalic anhy dridewith 4.7 parts of Larninopyridine and 100 parts of ethylene glycol isheated for 6 hours at ISO-160 C. with stirring..Aiter cooling, filteringoff the precipitate, washing with alcohol and drying, 13 parts of aproduct similar to that from Example 30 are obtained. v

On operating as in the preceding example, but replacingtheZ-aminopyridipe by equivalent quantities of the followingheterocyclic amines the corresponding 4- methoxy-naphthalimides areobtained:

NaphthallmldesoiFormula MP. 11 o 0.

Example 60 4 parts of sodium are dissolved in 200 parts by volume ofanhydrous ethyl alcohol in a round-bottomed flask provided with astirrer and a reflux condenser. 14.12 parts of4-bromo-N-(2-pyridyl)-naphthalimide are added and the mixture isrefluxed for 3 hours. After cooling, the precipitate is filtered oil,washed with a little alcohol, then with water until the filtrate isneutral, and dried. 4-ethoxy- N-(2-pyridyl)-naphthalimide of meltingpoint 232 C. is thus obtained.

Example 61 On replacing the 4-bromo-N-(2-pyridyl)-naphthalimide in thepreceding example by 13.7 parts of 4-bromo-N-(1,2,4-4H-triazol-3-yl)-naphthalimide, 4-ethoxy N (1,2,4-4H-triazol-3-yl)-naphthalimide of melting point 338 C. is obtained.

NAPHTHALIMID-ES OF FORMULA I Example 62 parts of methyl sulphate areintroduced into an apparatus provided with a stirrer and a thermometerand are heated to 100 C. and 10 parts of 4-methoxy-N-(2-pyridyl)-naphthalimide are then gradually introduced. The temperature ofthe mixture is raised to 130 C. and this temperature is maintained forabout an hour, until a sample taken is completely soluble in water. Theproduct is allowed to cool, diluted with 50 parts of water and left 6with-stirringtodecomposethe excess methyl sulphate. It is then boiledwith a little decolorizing charcoal and filtered. After cooling, 10parts of sodium chloride are added to the filtrate, then a dilutesolution of zinc chloridefuntil precipitation is' complete. Afterfiltering and drying the precipitate, 12 parts of the chlorozincate of4'- methoxy-2 naphthalimidol-methyl pyridinium monohydrate areobtained.After recrystallizing from water, analysis gives the following figures:

Calculated for C H N O Cl+ /zZnCl +H O (percent): C, 51.8; H, 3.86; N,6.36; Cl, 16.1. Found (percent): C, 51.96; H, 3.90; N, 6.70; Cl, 16.7.

I This product is in the form of a light beige crystalline powder, andisvery soluble in water. Its dilute aqueous solutions show an intense bluefluorescence.

Example 63 5.2 parts of 4-methoxy-N-(2-benzimidazolyl)-naphthalimide aredissolved in 25 parts of dimethyl formamide. 3 parts of methyl sulphateare added and the mixture is heated at 130 C. until a sample is solublein water. After cooling, 50- parts of water are added, the product isboiled with a little decolorizing charcoal and filtered. Sodiumchlorideis'added to the filtrate. A light yellow crystalline product isprecipitated. 5 parts of4-methoxy-2-naphthalimido-l,3-dimethyl-benzimidazolium chloride are thusobtained. After recrystallizing from water, analysis gives the followingresults:

Calculated for C H N O CLH O (percent): C, 62.06; H, 4.7; N, 9.87. Found(percent): C, 61.7; H, 5; N, 9.49.

This compound gives extremely fluorescent aqueous solutions.

v Example 64 8 parts of 4-methoxy-N- [4-(3,5-dimethyl-1-pyrazo1yl)-phenyn riaphthalimide (Example 47) are heated under reflux in parts byvolume of chlorobenzene and 5 parts of methyl sulphate are introduced ina period of an hour. The mixture is boiled for 2 hours and the solventis removed by steam distillation. The solution is treated with carbonblack, filtered, then cooled. The chlorozincate of"-methoxy-4'-naphthalimido-l-phenyl 2,3,5 trimethylpyrazolium isprecipitated by the addition of salt and a solution of zinc chloride.

Example 65 3 parts of 4 methoxy-N-(1,2,4-4H-triazol-4-yl)-naphthalimidefrom Example 51 are gradually introduced into 5 parts of ethyl sulphateheated to C. This temperature is maintained until a sample is soluble inwater. The mass is dissolved in water. The solution is boiled withdecolorizing charcoal, filtered and sodium chloride and zinc chlorideare added to the cooled solution. 4'-methoxy-4-naphthalimido-l-ethyl-(or 2 ethyl)-triazolium chlorozincate is thusobtained in the form of a light yellow powder which is soluble in waterwith an intense blue fluorescence.

Examples 66 to 84 On operating in a similar way according to one of theprocesses described in Examples 62, 63 and 64 the salts (chlorozincateor methyl sulphate) of other cycloammonium derivatives of Formula I areobtained from 4- al-koxynaphthalimides of Formula II and previouslydescribed.

N aphthalimlde oi FOl'mllll} Ex. Example- Naphthallmlde of Formula I 66.33 4' -methoxy-2-naphthallmldo-1, fi-dimethylpyrldlnlum (chlorozlncate).67.... 34 4-methoxy-2-na hthalimldo-ii-methyl-thiazollum (chlorozlneate68- 35 4-methoxy-2-naphthallmido-3, -dlmethylthiazolium (ehlorozlneate).69-..-.. 55 4'-methoxy-fi naphthallmldo-2-phenyl-3methylbenzothlazollnm(ehlorozincate). 70. 59 4-methoxy-2-naphthallmldo-l, 4-dlmethy1-quinolium (chlorozincate). 71. s 58 4-methoxy-6-naphthalimido-1,2-dlmethy1- qulnolium (ehlorozincate). 72. 37 4-methoxy-6-naphthallmido-1, 2, a-tnmethylbenzimidazolium(chlorozlncate). 73- 38 4 -methoxy-4 -naphthalimido-2-phenyl-1, 3-

dlmethyl-benzimidazolium (ehlorozineate). 74.. 404'-methoxy-fi-naphthalimldo-l, 2-dimethyllndazolium (chlorozincate) 75.43 4-methoxy-3-naphthalimido-4-phenyl-l, 2-

dlmethyl-pyrazolium (methyl sulphate). 76. 444-methoxy-3-naphthalimido-5-pheny 14, 2-

dlmethyl-pyrazollum (chlorozincate). 77-... 454'-methoxy-3-naphthalimido4-phenyl-1 2, 5-trimethyl-pyrazollum (methylsulphates. 78- 31 4 -Inethoxy-4-naphthallmldo-1, 2, 3,fi-tetramethylpyrazolium (chlorozlncate). 79.... 464-methoxy-4-naphthallmido-5-phen l-1,2,3-tnmethyl-pyrazolium(chlorozlncate 80. 47 4"-methoxy-4-naphthalimido'1-phenyl-2, 3,5-trlmethyl-pyrazollum (ehlorozineate). 81 494'-methoxy-3-naphthallmido-2, 4-dlmethyl-trla- Zolium (chlorozlncate).82. 50 4-methoxy-3-naphthallrnido-5-phenyl-2, 4-dlmethyl-triazolium(ehlorozincate). 83. 51 4 -methoxy-4-naphthallmido-1 (or 2)-methyltriazollum (ehlorozincate). 84. 524-meth0xy-4-naphthalimido-3-phenyl-2, 4, 5-

trlmethyl-trlazolium (ehlorozincate).

Example A treatment bath is prepared with 3000 parts of water, 3 partsof acetic acid and 0.4 part of the benzimidazolium salt of Example 63.It is heated to 40-50 C. and

parts of an Orlon fabric are introduced. The bath is heated to boilingand maintained at this for an hour. The fabric is removed, rinsed anddried. It has attained a remarkable whiteness. The same elfect isobtained on a fabric where the Orlon fibres have been replaced byCourtelle, Crylor or Dralon fibres.

8 Example 86 in which R is an alkyl group having from 1 to 4 carbonatoms, X is methyl or ethyl, Y is hydrogen or methyl, and A is acolorless monovalent anion.

methylthiazolium in which the anion is a colorless mono- 2. The salts of4' methoxy 2 naphthalimido-3,4-divalent anion.

3. The salts of 4' methoxy-Z-naphthalimido-3-methyl thiazolium in whichthe anion is a colorless monovalent anion.

References Cited UNITED STATES PATENTS 3 /1967 Kasai 260-281 5/ 1967Grogan 260-281 7/ 1967 Senshu 260281 3/ 1972 Mingasson 260-281 V12/ 1971Klein 260-281 OTHER REFERENCES Rice et al.: Jour. Med. Chem., vol. II,p. 183-5 v(.lan-

35 uary 1968).

DONALD G. DAUS, Primary Examiner

